TW201301622A - Improved lead-acid battery formulations containing discrete carbon nanotubes - Google Patents

Abstract

Compositions of discrete carbon nanotubes for improved performance lead acid batteries. Further disclosed is a method to form a lead-acid battery with discrete carbon nanotubes.

Description

Improved lead acid battery formulation with dispersed carbon nanotubes

This application claims the U.S. Provisional Patent Application Serial No. 61/500,561, filed on Jun. 23, 2011, entitled "Lead-acid battery formulation containing dispersed carbon nanotube fibers"; and April 25, 2012 The U.S

The present invention relates to a novel composition and method for producing a lead-acid battery, wherein the composition contains dispersed carbon nanotubes or dispersed carbon nanotubes and graphene or oxidized graphene sheets. mixture.

Carbon nanotubes can be classified into single wall, double wall and multi wall by the number of walls in the tube. Each wall of the carbon nanotube can be further classified into a palmar or non-palmative form. The carbon nanotubes are now made into agglomerated nanotube spheres or bundles. In general, the use of carbon nanotubes and graphene in batteries as a performance enhancing additive is expected to have significant utility for electric vehicles and power storage. However, the use of carbon nanotubes is hindered in these applications due to the general inability to reliably manufacture individualized carbon nanotubes.

The performance goal of lead-acid batteries is to maximize specific power (measured per watt of power per kilogram of watts per kilogram of power) in the designed high-rate discharge scheme, and to maximize battery life (not only in terms of environmental durability) And the heaviest Also in the cycle life (number of possible charges / discharges)).

Corrosion (on the positive plate) and sulfation (on the negative plate) define two key failure modes for lead-acid batteries to date. In view of corrosion failure, this failure mode begins to accelerate when the temperature rises by about 70 °F and/or if the battery stays in discharge. In order to mitigate the effects of the corrosion process, most battery companies have focused their research on the development of more corrosion-resistant lead alloys and grid fabrication methods that reduce mechanical stresses in the grids produced. Regardless of the alloy or grid manufacturing process, substantially all battery manufacturers plan the useful life of the battery based on the lead alloy and grid cross-sectional area. Normally, this plan translates into varying grid thickness and corresponding board thickness. Thicker grids provide longer life, but typically sacrifice power density, cost, weight, and volume.

Considering the failure of sulfation, when the lead-acid battery is parked in the open position or maintained in a partial or complete discharge state for a period of time, the lead sulfate formed in the discharge reaction will recrystallize to form a large low surface area lead sulfate crystal ( It is often referred to as hard lead sulfate). This low surface area, non-conductive lead sulfate can hinder the conduction path required for recharging. These crystallizations (especially those most difficult to remove from the electrode grid) are difficult to convert back into the charged lead and lead dioxide active materials. Even a well-maintained battery will lose some capacity over time due to the continuous growth of large lead sulfate crystals, which are not fully recharged during each recharge. These sulfate crystals have a density of 6.287 g/cm 3 and a volume of about 37% that of the original paste, so they mechanically deform and push the sheet apart. The resulting plate expansion and deformation also results in separation of the active material from the electrode and a commensurate performance loss. Sulfation is a major problem during battery storage during the end of the season in casual applications. Boat, motorcycle The trolley and the snowmobile suspend the activity during the month in which they are not in use, and stop discharging without charging, toward the zero-state state of charge, which causes the battery to gradually sulfate. Therefore, the battery can no longer be recharged, irreversibly damaged, and must be replaced.

Because users already know the portable battery products in mobile phones and laptops, people have become comfortable to let the battery use almost no power, and then let it return to the maximum, fully charged within a few hours. And the process of power capacity. Conventional lead-acid batteries, due to their inherent design and active material usage limitations, provide a relatively good cycle life only when consumed less than about 80% of the rated capacity during each discharge event in the application. This type of battery is significantly reduced in the number of discharges and recharges (i.e., cycle life) when it consumes 100% of the rated capacity during a single discharge in an application. Many new products of lead-acid batteries used in the past require a significant jump cycle life. The most obvious embodiment is a hybrid electric vehicle that operates in a high rate partial-state-of-charge condition. This is a large-scale consumable application that dramatically shortens the cycle life of typical lead-acid batteries, thus giving automakers no choice but to move to more expensive nickel metal hydride batteries and experiment with lithium-ion batteries.

Typically, lead acid batteries require significantly longer recharge times than competing batteries containing advanced materials found in portable products. Lead-acid battery charging (such as in an electric vehicle) can take 8 to 16 hours to complete. In the case of an uninterruptible power system (UPS), when charging is delivered for use on the initial battery, the fast charge rate is the basis for ensuring quality performance and reducing the capital/consumption associated with the backup device.

Environmental conditions (such as vibration) can also lead to lead-acid batteries due to active materials Degraded from the cathode or anode and degraded. More vibration resistant batteries, such as those used in cruise ships, often include thicker electrodes or special damping structures within the battery. This increases the weight and cost of the battery. Therefore, increasing the mechanical strength of the active material paste will be a highly desirable feature.

Conventional methods for fabricating lead plates for lead acid batteries typically include mixing, hardening, and drying operations in which the active materials in the battery paste undergo chemical and physical changes that are used to establish chemical and physical structures and subsequently form the panels. Mechanical strength. To make a typical panel, the material is added to the commercial paste mixing machine common in the industry in the order of lead oxide, fluff, water and sulfuric acid, and then mixed to the paste consistency. The flock component is a fibrous material typically composed of polyester, nylon or acrylic fibers that is selectively added to the paste to increase the mechanical strength of the pasted board. Conventionally, an "expander" component is added to a negative paste consisting of a mixture of barium sulfate, carbon black, and lignosulfonate, which is added to the negative paste to improve battery performance and cycle life. During the mixing, a chemical reaction takes place in the paste to produce basic lead sulphate, the most common being tribasic lead sulphate. The final paste composition is a mixture of basic lead sulfate, unreacted lead oxide and residual free lead particles. Paste is a method of manufacturing a panel. This paste is dispersed into a commercial automatic pasting machine of the type commonly used in the industry, which coats the paste to a grid structure composed of a lead alloy at a high speed. The paste is typically dried in a tunnel dryer of the type commonly found in the industry and then stacked into columns or placed on a rack. The stack or rack plate is then placed in a hardened chamber. During the entire paste and hardening operation, it is very important that the paste has sufficient mechanical strength to avoid microcrack formation, thus increasing Add the internal resistance of the paste mixture. High internal resistance limits discharge and charge rates and causes localized heating during charging/discharging and increases chemical degradation of active species.

In an effort to reduce the high impedance of the battery to accelerate the formation (first charging) step, carbon black has been added to the paste. However, for proper dispersion, carbon black surfactants are used, but these surfactants produce higher impedance, which is difficult to reduce for carbon black particles. Also, since there is often a high-impedance region due to the uneven contact resistance of the powder, an overvoltage is often applied, which causes water to be electrolyzed to generate oxygen at the cathode, and then rapidly degrade the carbon black. It is highly desirable to have a method of reducing the resistance of the lead acid battery to avoid overvoltage requirements for charging and permanent conductive additives to the cathode.

The present invention is directed to a lead acid battery comprising a plurality of dispersed carbon nanotube fibers having a depth ratio of from about 10 to about 500 and optionally having the dispersed carbon nanotubes having open ends. The carbon nanotube fibers can comprise a degree of oxidation of from about 1 weight percent to about 15 weight percent. The plurality of dispersed carbon nanotubes may comprise at least one surfactant or dispersion aid comprising a sulfate moiety. The composition of the oxidized and dispersed carbon nanotubes can be dispersed in water to produce a extender material and/or a battery paste.

A further aspect of the invention is a battery paste material for a lead acid battery comprising a plurality of dispersed carbon nanotubes having an aspect ratio of from about 10 to about 500, preferably from about 25 to about 250, of an organic material And optionally at least one inorganic salt (such as barium sulfate, tetrabasic lead sulfate, calcium sulfate or oxidation) Tin), and optionally at least one non-fibrous carbon fraction (such as graphite, graphene, graphene sheets, functionalized graphene, oxidized graphene or carbon black). The organic material may comprise a sulfonated polymer, preferably selected from the group consisting of sulfonated polymers (including but not limited to lignosulfonates, sulfonated polystyrenes) or sulfonated polymers thereof. A group of combinations.

Another aspect of the present invention is a method of forming a lead-acid battery, the steps comprising: a) selecting a carbon nanotube tube having a dispersion ratio of about 10 to 500 in depth; b) selecting a degree of oxidation of from 1 to 15% by weight. a dispersed carbon nanotube fiber; c) selecting a dispersed carbon nanotube having at least a portion of the open terminal tube; d) blending the fiber with a liquid to form a liquid/fiber mixture; e) selectively binding the fiber a liquid/fiber mixture and a sulfonated polymer; f) selectively adjusting the pH to a desired degree; g) selectively combining the liquid/fiber mixture with at least one surfactant; h) agitating the liquid/fiber mixture to a degree sufficient to disperse the fibers to form a liquid/dispersed fiber mixture; i) selectively bind the liquid/disperse fiber mixture to at least one inorganic salt; j) selectively bind at least one non-fibrous carbon portion; k) selectively dry the fiber a dispersed fiber mixture; and 1) combining the dispersed carbon nanotube fiber/composite mixture with the lead-containing component to form a battery paste mixture. This agitation step h) is preferably performed using ultrasonic waves.

A further aspect of the present invention is that the carbon nanotube fibers can be bonded or coated with at least one electrically conductive polymer, preferably selected from the group consisting of conductive polymers: polyaniline, polyphenylene extended ethylene Base, polyvinylpyrrolidone, polyacetylene, polythiophene, polyphenylene sulfide, blends thereof, copolymers and derivatives thereof.

One embodiment of the invention is a battery having at least one layer comprising dispersed carbon nanotube fibers.

Another embodiment of the invention is a battery paste comprising dispersed carbon nanotubes that exhibits at least those paste counter electrodes (such as carbon/lead and other lead or carbon type electrodes) that are free of carbon nanotubes. 10% improved adhesion.

A further embodiment of the invention is a battery comprising a dispersed carbon nanotube that exhibits an electrolyte concentration provided at any temperature as compared to those without a carbon nanotube at the same electrolyte concentration and temperature. There is at least a 10% increase in ion transport.

A further embodiment of the present invention is a negative electrode for an energy storage device comprising: a current collector; a corrosion-resistant conductive coating that firmly grips at least one side of the current collector; a carbon particle and a sheet of carbon nanotube fibers comprising from 1 to 15 weight percent of oxidized species and having a depth ratio of from about 10 to about 500, the sheet being adhered to the corrosion-resistant conductive coating; one extending from one side of the negative electrode a protruding portion; a handle comprising a lead or a lead alloy enclosing the protruding portion; and a cast-on strap selectively comprising the lead or lead alloy and Wrap at least part of the handle.

Another aspect of the present invention is a lead-acid battery, wherein at least one of the electrode cell pastes has a gradient concentration of dispersed carbon nanotubes throughout the thickness of the paste, selectively at the surface of the current collector or at the separator The highest material concentration is at the surface.

A further aspect of the present invention is a lead acid battery comprising a dispersed carbon nanotube that is equipped with an energy regenerative braking system useful for improving fuel efficiency It is useful for vehicles that start or stop technology. They can also be useful for uninterruptible power systems and power.

In the following description, some details are set forth, such as specific quantities, dimensions, etc., in order to provide a complete understanding of the specific embodiments disclosed herein. However, it will be apparent to those skilled in the art that the present disclosure may be practiced without the specific details. In many instances, details of such considerations and similar scenarios have been omitted, as such details are not necessary to fully understand the disclosure and are within the skill of those of ordinary skill in the art.

Although most of the terms used herein will be recognized by those of ordinary skill in the art, it should be understood that, when not explicitly defined, the term should be used in a manner that is currently recognized by those of ordinary skill in the art. To explain. In cases where the interpretation of the term would provide meaningless or essentially meaningless, the definition should be taken from Webster’s Dictionary, 3rd edition, 2009. Definitions and/or clarifications should not be taken from other patent applications, patents or announcements, or related, unless otherwise specifically stated in this patent specification or if the incorporation is maintained as correct. The depth ratio is the ratio of the length divided by the diameter (L/D), where the length and the diameter are selected in the same unit, so the unit is eliminated as a ratio, and the depth ratio is made to have no unit value.

For a positive paste mixture of automobiles, the specific gravity of sulfuric acid in the mixture examples is preferably about 1.400 and the paste density is typically in the range of from about 4.15 to 4.27 grams per cubic centimeter. For car's negative paste mixture, sulfuric acid The specific gravity is preferably about 1.400 and the paste density is typically in the range of about 4.27 to 4.39 g/cm 3 . For industrial positive paste mixtures, the specific gravity of sulfuric acid is preferably about 1.400 and the paste density is typically in the range of about 4.33-4.45 grams per cubic centimeter. For industrial negative paste mixtures, the sulfuric acid specific gravity is preferably about 1.400 and the paste density is typically in the range of about 4.45-4.57 grams per cubic centimeter. The paste density is a measure of the composition of the paste and also its suitability for pasting by a commercial paste mixing machine. The "swarf" component is a fibrous material which typically consists of polyester, nylon or acrylic fibers which are selectively added to the paste to increase the mechanical strength of the pasted board. Conventionally, the "expander" component is a mixture of barium sulfate, carbon black and lignosulfonate which is added to the negative paste to improve the performance and longevity of the negative plate.

In various embodiments, a plurality of carbon nanotubes are disclosed, including having a depth ratio of from about 10 to about 500 (preferably from about 60 to about 200) and an oxidation degree of from about 1 weight percent to about 15 weight percent (preferably It is from about 2 weight percent to about 10 weight percent of single wall, double wall or multi-wall carbon nanotube fibers. The degree of oxidation is defined as the amount (by weight) of the species covalently bonded to the oxidation of the carbon nanotubes. The pyrolysis method for measuring the weight percentage of the oxidized species on the carbon nanotubes comprises removing about 5 mg of dry oxidized carbon nanotubes and from room temperature at 5 ° C/min in a large dry nitrogen atmosphere. Heat to 1000 degrees Celsius. A weight percent loss of between 200 and 600 degrees Celsius is used as a weight percent loss of the oxidized species. The oxidized species can also be quantified using Fourier transform infrared spectroscopy (FTIR), particularly in the wavelength range 1730-1680 cm ^-1 ; or by using energy dispersive x-ray measurements.

The carbon nanotube fibers may have an oxide species (a carboxylic acid or a species containing a carbonyl derivative) and are substantially unentangled dispersed individual fibers as a host. The carbonyl derivative species may include ketones, quaternary amines, guanamines, esters, mercapto halogens, monovalent metal salts, and the like.

The illustrative method used to make the dispersed oxidized carbon nanotubes is as follows: 3 liters of sulfuric acid (97 percent sulphuric acid and 3 percent water) and 1 liter of concentrated nitric acid (including 70 percent nitric acid and 30 percent water) are added to the 10 liter installation. A temperature-controlled reaction vessel for a sonic vibrator and agitator. 40 grams of undispersed carbon nanotubes (Grade Flow 9000 from CNano Corporation) were loaded into the reactor vessel while stirring the acid mixture and maintaining the temperature at 30 °C. The sonic vibrator power was set at 130-150 watts and the reaction was continued for three hours. After 3 hours, the viscous solution was transferred to a filter with a 5 micron filter mesh and more acid mixture was removed by filtration using a pressure of 100 psi. The filter cake was washed once with about four liters of deionized water, then four liters of ammonium hydroxide solution was washed once at a pH greater than 9, and then washed twice with four liters of deionized water. The final cleaning resulted in a pH of 4.5. The small filter cake sample was dried in vacuum at 100 ° C for four hours and subjected to thermogravimetric analysis as previously described. The amount of species oxidized on the fibers was 8 weight percent and the average depth ratio (as measured by scanning electron microscopy) was 60.

The dispersed oxidized carbon nanotubes (CNT) in a wet form were added to water to form a concentration of 1 weight percent, and the pH was adjusted to 9 using ammonium hydroxide. Sodium dodecylbenzene sulfonate was added at a concentration of 1.5 times the mass of the oxidized carbon nanotubes. The solution was sonicated while stirring until the CNTs were completely dispersed in the solution. When the UV absorption at a concentration of 2.5 x 10 ^-5 g CNT/ml at 500 nm is greater than 1.2 absorbance units, it is defined that each tube has sufficient dispersion.

An illustrative method for making a dispersed carbon nanotube/graphene composition is as follows: 3 liters of sulfuric acid (97% sulfuric acid and 3% water) and 1 liter of concentrated nitric acid (including 70% nitric acid and 30% water) are added to 10 The temperature is controlled in a reaction vessel equipped with a sonic vibrator and a stirrer. 20 grams of undispersed carbon nanotubes (Grade Flow 9000 from CNano Corporation) and 20 grams of expanded graphite (obtained from Rice University, Houston, Texas, USA) were loaded into the reactor vessel while stirring the acid mixture and The temperature was maintained at 25 °C. The sonic vibrator power was set at 130-150 watts and the reaction was continued for 3 hours. After 3 hours, the viscous solution was transferred to a filter with a 5 micron filter mesh and more acid mixture was removed by filtration using a pressure of about 100 psi. The filter cake was washed once with 4 liters of deionized water, followed by 4 liters of ammonium hydroxide solution washed once at pH > 9, and then washed two or more times with 4 liters of deionized water. The final cleaning produced a pH system > 4.5. The electron micrograph will show the graphene sheets interspersed with carbon nanotubes.

Cathode or negative active material paste

Control 1. 79.3 grams of lead yellow (lead (II) oxide) was mixed with 0.634 grams of sodium sulfate and 0.793 grams of extender material (Hammond, grade 631). 9.28 grams of water was combined with 0.397 grams of Teflon emulsifier (Du Pont, grade K20) and added to the mixture containing lead yellow. Then, slowly add 17.08 grams of sulfuric acid (specific gravity 1.4) while mixing and maintaining the temperature between 49 and 54 degrees Celsius. Finish The mixture was thoroughly mixed. The paste had a density of 63.2 g/cubic inch.

Example 1

A negative active paste material was prepared as in Comparative Example 1, except that the extender material included dispersed carbon nanotubes prepared as follows. Ten grams of Hammond Expander 631 (which contains lignosulfonate, barium sulfate, and carbon black) was added to 200 cubic centimeters of deionized water. 0.25 grams of carbon nanotubes that had been oxidized to about 6% by weight were added and then ultrasonically treated in a sonic vibrator bath for 30 minutes. The mixture comprising the carbon nanotubes is then dried to provide a free flowing powder.

Anode or positive active material paste

Control 2. 75.7 grams of red dan (lead (III) tetraoxide) was mixed with 0.6056 grams of sodium sulfate. 14.83 grams of water was combined with 0.389 grams of Teflon emulsifier (Du Pont, grade K20) and added to the mixture containing lead yellow. Then, slowly add 15 grams of sulfuric acid (specific gravity 1.4) while mixing and maintaining the temperature between 49 and 54 degrees Celsius. The mixture was thoroughly mixed. The paste has a density of 60.78 g/cubic inch.

Example 2

The lead cathode and the anode film of the interspersed glass fiber mat were uniformly coated with a negative and positive paste, respectively, and then a sulfuric acid having a specific gravity of 1.12 was charged to construct a single battery. The negative paste has 0.05% by weight of carbon nanotubes (relative to the starting lead oxide).

Control 3. Spreading the scattered glass evenly by negative and positive paste separately The lead cathode and anode film of the fiber mat are then filled with sulfuric acid having a specific gravity of 1.12 to construct a single battery. The negative paste does not contain a carbon nanotube.

The battery of Control 3 was measured to have an internal resistance of 100 ohms. The battery of Example 2 containing the dispersed carbon nanotubes was measured to have an internal resistance of 50 ohms.

Example 3

The lead cathode and the anode film of the interspersed glass fiber mat were uniformly coated with a negative and positive paste, respectively, and then a sulfuric acid having a specific gravity of 1.12 was charged to construct a single battery. The positive and negative pastes had 0.16 wt% carbon nanotubes (relative to the starting lead oxide). The paste of Example 3 was observed to be easier to handle and transferred to the lead current collector plate without damage (cf. Control 3).

A typical current limiting first charging cycle, shown in Figure 1 for Controls 3 and 3, is shown. Although the current curve was the same in each case, the voltage of Example 3 was low, and this example shows that Example 3 containing the carbon nanotube of the present invention has a lower impedance than Control 3. Further, in Example 3, the overvoltage of water electrolysis was avoided in comparison with Control 3. Also seen in Figure 1, the benefit of the embodiment having a lower voltage but a higher current (compared to the control) can be seen when discharging the battery at a rate that will fully discharge within 3 hours.

The results shown in Fig. 2 are the results of charging Example 3 and Control 3 in two steps at a fixed voltage. After 2 hours, the voltage was increased to 2.3 volts. Example 3 was able to absorb higher currents than Control 3 and was fully chargeable. Example 3 provides the expected discharge curve at the time of discharge, whereas control 3 has It is considered to be damaged. The results of Example 3 are considered to be consistent with pastes having improved and more uniform electrical conductivity.

Shown in Fig. 3 is an electron micrograph of the dry anode material of Example 3 after 14 charge/discharge cycles. At the 14th discharge, it was discharged to 1.75 volts, i.e., incompletely discharged, so there were two crystal forms (lead and lead sulfate) as illustrated in Fig. 3. It can be seen that the carbon nanotubes of the present invention are very well interspersed between the lead particles. It can be seen that lead sulphate crystals are incorporated into the carbon nanotubes of the present invention.

The electron micrograph of the dry cathode material of Example 3 in Figure 4 after 14 charge/discharge is shown. At the 14th discharge, it was discharged to 1.75 volts, i.e., incompletely discharged, so there were two crystal forms (lead dioxide and lead sulfate) as illustrated in Fig. 4. It can be seen that the carbon nanotube of the present invention is incorporated into the crystals of lead dioxide and lead sulfate. This clarifies that the carbon surface is protected by lead dioxide or lead sulfate, and thus it is expected that there will be less tendency to oxidize attack if electrolysis occurs by overvoltage.

Figure 1 shows a graph of the charge of a lead-acid battery (Example 3) containing a carbon nanotube according to the present invention at a constant current intensity, and a carbon nanotube (Control 3) not containing the present invention; Figure 2 shows a charge profile of a lead acid battery (Example 3) containing a carbon nanotube according to the present invention at a constant voltage, and a carbon nanotube (Control 3) not containing the present invention.

Figure 3 shows the dry anode material of Example 3 at 14 charge/discharge Electron micrograph after electrical cycling.

Figure 4 shows an electron micrograph of the dry cathode material of Example 3 after 14 charge/discharge cycles.

Claims (18)

A composition for a lead acid battery structure comprising: a plurality of dispersed carbon nanotube fibers having a depth ratio of from about 10 to about 500; wherein the dispersed carbon nanotubes are open ended. The composition of claim 1, wherein the carbon nanotube fibers have an oxidation degree of from about 1 weight percent to about 15 weight percent. The composition of claim 1, further comprising at least one surfactant or dispersion aid, wherein the surfactant or dispersion aid comprises a sulfate moiety. The composition of claim 1, further comprising water, wherein the nanotube fibers are dispersed in water to form an expander material or a battery paste. The composition of claim 3, wherein the surfactant or dispersion aid is selected from the group consisting of sulfonated polymers consisting of lignosulfonates, sulfonated polystyrenes, and combinations thereof. . A material for a battery paste for a lead-acid battery, comprising: a plurality of dispersed carbon nanotube fibers having a depth ratio of about 10 to about 500; an organic material; Inorganic salts; and non-fibrous carbon fractions. The composition of claim 6, wherein the inorganic salt is selected from the group consisting of barium sulfate, lead sulfate, calcium sulfate, and tin oxide. The composition of claim 6, wherein the non-fibrous carbon portion is selected from the group consisting of carbon black, graphite, and graphene. A method for producing a lead-acid battery material, the steps comprising: (a) selecting a carbon nanotube tube having a dispersion ratio of 10 to 500 in depth; (b) selecting a dispersed carbon having a degree of oxidation of 1 to 15% by weight a tube of carbon nanotubes; (c) a dispersed carbon nanotube having a tube having at least a portion of an open terminal; (d) blending the fiber with a liquid to form a liquid/fiber mixture; (e) combining the liquid/fiber Mixing the sulfonated polymer; (f) adjusting the pH to a desired degree; (g) combining the liquid/fiber mixture with at least one surfactant; (h) agitating the liquid/fiber mixture to sufficiently disperse the fiber To the extent that a liquid/dispersed fiber mixture is formed; (i) combining the liquid/dispersed fiber mixture with at least one inorganic salt to form a fiber/salt mixture; (j) combining a non-fibrous carbon portion with the fiber/salt mixture to form a fiber/non-fibrous carbon mixture; (k) drying the fiber/non-fibrous carbon mixture; and (1) combining the fiber/non-fibrous carbon mixture with The lead component is formed to form a battery paste mixture. A battery comprising the material of item 1 of the scope of the patent application. The composition of claim 1 further comprises a conductive polymer selected from the group consisting of polyaniline, polyphenylene vinylene, polyvinylpyrrolidone, polyacetylene, polythiophene, poly Phenylene sulfide, blends, copolymers and derivatives thereof. A battery paste comprising the material of claim 1, wherein the battery paste has at least 10% improved adhesion to a carbon/lead electrode, a lead electrode or a carbon electrode than a paste without a carbon nanotube. A battery comprising the material of claim 1 wherein the battery paste provides an electrolyte concentration at any temperature for ion transport at a same electrolyte concentration and temperature as the battery without the carbon nanotube tube. Has a 10% or greater increase. A negative electrode for an energy storage device, comprising: a current collector; a corrosion-resistant conductive coating that firmly grips at least one side of the current collector; a sheet comprising carbon particles and carbon nanotube fibers, wherein the carbon nanotube fibers comprise from 1 to 15 weight percent of oxidized species and Having a depth ratio of from about 10 to about 500, wherein the sheet adheres to the corrosion-resistant conductive coating; a raised portion extending from one side of the negative electrode; a handle comprising lead or lead alloy, which surrounds the protrusion a portion; and a cast metal strip comprising a lead or lead alloy on the handle that encases at least a portion of the handle. A lead-acid battery comprising the composition of claim 1, wherein at least one of the electrodes comprises a battery paste having a concentration gradient across the thickness of the battery paste as in the first aspect of the patent application. A lead acid battery according to claim 15 wherein the highest concentration of the composition as claimed in claim 1 is at the surface of the current collector or at the surface of the separator. A use of a lead acid battery composition as claimed in claim 1 for use in a vehicle equipped with an energy regenerative braking system or a start-stop technique for improving fuel efficiency. A composition for a lead-acid battery as claimed in claim 1 It is used in the continuous power supply and power smoothing.